1. Technical Filed
The present invention relates to novel water-soluble polyurethane having a comb-shaped hydrophobic group.
The present invention also relates to an extruding auxiliary using the above novel water-soluble polyurethane, an extruding composition of a cement material containing the extruding auxiliary, and extruded forms of a cement material having improved strength obtained by extruding the above extruding composition of a cement material. The present invention further relates to a novel thickening agent for a mortar available for widely varying types of mortar such as repairing mortar, tile-bonding mortar, masonry mortar, spraying mortar, substrate mortar and topping mortar. The present invention further relates to a novel thickening agent for an underwater concrete and a composition for an underwater concrete containing the novel thickening agent for an underwater concrete. The present invention further relates to a novel ceramics forming binder. And the present invention further relates to a novel moisturizer for hair cosmetics excellent in moisture retention to hair.
2. Background Art
When extruding a mortar comprising a cement, a fine aggregate, a fiber and water with a vacuum extruder or the like to produce cement plates extruding the same, in order to extrude the mortar without separating water therefrom, in other words, in order to impart water retention to the mortar, there has been a need to add a water-soluble polymer to the mortar (refer to, for example, Japanese Patent Publication No. 43-7134). In order to develop sufficient water retention, the aqueous mortar solution needs to have a high viscosity, and water-soluble cellulose ethers such as methyl cellulose (MC), hydroxypropyl methyl cellulose (HPMC) and hydroxyethyl cellulose (HEC) are mainly used as the water-soluble polymer at present.
In order to retain the shape of extruded forms immediately after extrusion, in other words, in order to impart shape retention to mortar, the mortar needs to exhibit excellent thixotropic properties; and, it was not sufficient to impart shape retention thereto by an addition of only the water-soluble polymer such as methyl cellulose to the mortar. Thus, asbestos has been used in combination with water-soluble cellulose ethers (refer to, for example, Japanese Patent Publication No. 43-7134).
So, in the conventional extrusion process, the requirements of water retention and shape retention of mortar in extruding mortar have been satisfied by the use of asbestos in combination with water-soluble cellulose ethers.
In recent years, however, the harmfulness of asbestos has been pointed out and restrictions have been imposed on its use. As a result, the fibers such as various types of polymer fibers and glass fibers have become in use as substitutes for asbestos. The mortar using these asbestos-substitute fibers is, however, inferior in shape retention to the mortar using asbestos. Thus, there have been demands for the development of novel extruding auxiliary capable of imparting water retention as well as sufficient shape retention to mortar with the use of asbestos-substitute fibers.
On the other hand, the water-soluble cellulose ethers have a problem that they are likely to trap bubbles when mixing mortar, and due to the bubbles, the strength of the extruded forms of the mortar is likely to decrease.
In addition, the water-soluble cellulose ethers are relatively expensive because they are semisynthetic polymers produced from special natural wood pulp as a raw material and boost the raw material costs of the extruded forms. Furthermore, the natural wood pulp as resources is limited. Thus, a novel extruding auxiliary has been desired which can be synthesized from less expensive industrial materials.
Under those circumstances, the present inventors found an extruding auxiliary which is synthesized using polymer having a comb-shaped hydrophobic group (Japanese Patent Application Laid-Open No. 10-298261); however, the extruding auxiliary had a problem of its solubility.
The mortar having cellulose ether added thereto is not limited to the extruding mortar as described above, and various types of mortar have been used, wherein the mortars are thickened by the addition of cellulose ether thickening agents so as to improve its workability and prevent bleeding from occurring.
The cellulose ether mortar thickening agents (specifically, methyl cellulose, hydroxypropyl methyl cellulose, hydroxyethylmethyl cellulose, hydroxyethyl cellulose, hydroxyethylethyl cellulose, etc.) impart moderate thixotropic properties as well as water retention to mortar to be useful for improvement in workability (for example, making trowelling easier) and for prevention of bleeding. However, they have a disadvantage of inhibiting hydration reaction of mortar, and hence retarding curing time. This has caused problems of making curing time longer in particular under low temperature conditions (for example, outdoors in the winter) and making the mortar strength insufficient.
When placing concrete under water, it is also known that a water-soluble thickening agent is added to the concrete as an underwater anti-separating agent in order to avoid the separation of its mortar and aggregate under water (for example, Japanese Patent Application Laid-Open No. 57-123850). In order for the thickening agent to develop sufficient underwater anti-separating properties, the aqueous solution needs to have a high viscosity; thus, as the polymers for thickening agents, water-soluble cellulose ethers such as methyl cellulose (MC), hydroxypropyl methyl cellulose (HPMC), hydroxyethyl methyl cellulose (HEMC) and hydroxyethyl cellulose (HEC) are widely used at present.
The water-soluble cellulose ethers, however, have a problem of retarding the curing time of concrete (retarding setting) which may make the concrete strength easier to decrease.
Further, the water-soluble cellulose ethers have problems in terms of their costs and raw material supply since they are semisynthetic polymers, as described above. Thus, a novel thickening agent for an underwater concrete, which can be synthesized from less expensive industrial materials, has been desired.
In the forming of ceramics, particularly in extrusion of ceramics, an extrusing binder composed of a water-soluble polymer is blended so as to impart sufficient plasticity, tackiness and lubricating properties to the green sand, and various types of cellulose ethers such as methyl cellulose (MC) and hydroxypropyl methyl cellulose (HPMC) are widely used as the polymers.
The cellulose ethers, however, have a problem that their heat release in degreasing is rapid and the heat release value is high, therefore, the extruded forms are likely to be damaged at the time of degreasing. Furthermore, it is also a problem that carbonized residues or carbonized inorganic salts are likely to remain after degreasing (high carbon residue content).
Hair cosmetics such as hair conditioner, hair gel, hair foam, shampoo and rinse require moisturizer, which contains water-soluble polymer, so as to create moist feel. And, as the polymers for such cosmetics, water-soluble polymers such as polyethylene glycol (PEG) or various types of cellulose ethers are widely used at present.
However, for polyethylene glycol, it has a problem of creating a sticky hair impression, but not creating moist feel. At the same time, cellulose ethers such as hydroxyethyl cellulose (HEC) also have a problem of creating a stiffed hair impression, but not creating moist feel.
An object of the present invention is to provide novel water-soluble polyurethane having a comb-shaped hydrophobic group.
Another object of the present invention is to provide a novel extruding auxiliary to replace water-soluble cellulose ethers which is more economical, is capable of imparting excellent shape retention to mortar and excellent strength of the extruded forms of mortar, and has an improved solubility. Still another object of the invention is to provide an extruding composition of a cement material, wherein the composition has excellent shape retention, excellent strength, and is improved in solubility. Another object of the invention is to provide extruded forms of a cement material whose strength is improved.
Further object of the present invention is to provide a novel thickening agent for a mortar to replace the cellulose ether mortar thickening agents, wherein the thickening agents is available for widely varying types of mortar such as repairing mortar, tile-bonding mortar, masonry mortar, spraying mortar, substrate mortar and topping mortar.
Furthermore, an object of the present invention is to provide a novel thickening agent for an underwater concrete to replace water-soluble cellulose ethers, wherein the thickening agent is more economical and excellent in underwater anti-separating properties, and is improved in retardation of setting.
Another object of the invention is to provide a novel ceramics forming binder to replace cellulose ethers whose heat release in degreasing is slow, heat release value is low, and carbon residue content is also low.
Still another object of the present invention is to provide a novel moisturizer for a hair cosmetic to replace PEG or cellulose ethers which imparts water retention to hair and creates excellent moist hair impression.
After concentrating their energies on solving the aforementioned problems, the present inventors found novel water-soluble polyurethane having a comb-shaped hydrophobic diol as an associating group, said diol having a dispersion degree almost corresponding to a monodispersed system, which led to their completion of the present invention.
Specifically, the present invention with which can achieve the above objects is characterized as described below.
A water-soluble polyurethane according to the present invention is a polymer comprising a repeating unit (U-1) represented by the following general formula (1): 
and a repeating unit (U-2) represented by the following general formula (2): 
wherein a molar ratio of the repeating unit (U-1) is 0.5 or higher and 0.999 or lower, a molar ratio of the repeating unit (U-2) is 0.001 or higher and 0.5 or lower, and weight average molecular weight, as determined by gel permiation chromatography (GPC), is in the range of 10,000 to 10,000,000. In the above formula,
A is a bivalent group such that HO-A-OH is water-soluble polyalkylene polyol having hydroxyl groups at least on both its ends and having a number average molecular weight of 400 to 100,000 (compound A);
B is a bivalent group such that OCNxe2x80x94Bxe2x80x94NCO is a polyisocyanate compound selected from the group consisting of polyisocyanates whose total number of carbon atoms is 3 to 18 (compound B); and
D is a bivalent group such that HO-D-OH is comb-shaped hydrophobic diol having the following general formula (3) (compound D): 
wherein R1 is a hydrocarbon group or a nitrogen-containing hydrocarbon group of 1 to 20 carbon atoms; each of R2 and R3 is a hydrocarbon group of 4 to 21 carbon atoms; fluorine, chlorine, bromine or iodine may be substituted for part of or all of the hydrogen atoms of the hydrocarbon groups R1, R2 and R3; R2 and R3 may be the same or different from each other; each of Y and Yxe2x80x2 is hydrogen, a methyl group or a CH2Cl group; Y and Yxe2x80x2 may be the same or different from each other; each of Z and Zxe2x80x2 is oxygen, sulfur or a CH2 group; Z and Zxe2x80x2 may be the same or different from each other; n is an integer of 0 to 15 when Z is oxygen and is 0 when Z is sulfur or a CH2 group; nxe2x80x2 is an integer of 0 to 15 when Zxe2x80x2 is oxygen and is 0 when Zxe2x80x2 is sulfur or a CH2 group; and n and nxe2x80x2 may be the same or different from each other.
The molar ratio of the above repeating unit (U-1) is preferably 0.5 or higher and 0.99 or lower, the molar ratio of the above repeating unit (U-2) is preferably 0.01 or higher and 0.5 or lower, the above compound A is polyethylene glycol whose number average molecular weight is 3,000 to 20,000, the above compound B is a diisocyanate compound selected from the group consisting of aliphatic diisocyanates whose total number of carbon atoms is 3 to 18, and the water soluble polyurethane has a weight average molecular weight, as determined by GPC, in the range of 100,000 to 1,000,000.
The above compound D may be comb-shaped hydrophobic diol having the following formula (4): 
wherein R1xe2x80x2 is a chain alkyl group having 4 to 18 carbon atoms, each of R2 and R3 is an alkyl group or aryl group having 4 to 18 carbon atoms, the total number of carbon atoms of R1xe2x80x2, R2xe2x80x2 and R3xe2x80x2 is 12 to 40, and R2xe2x80x2 and R3xe2x80x2 are the same.
Further, the above compound D may be comb-shaped hydrophobic diol having the following formula (5): 
wherein R8 and R9 are hydrocarbon groups, the total number of carbon atoms of R8 and R9 being 2 to 20; R10 and R11 are hydrocarbon groups each of 4 to 21 carbon atoms; fluorine, chlorine, bromine or iodine may be substituted for part of or all of the hydrogen atoms of the hydrocarbon groups R8, R9, R10 and R11; R8 and R9 may be the same or different from each other; R10 and R11 may be the same or different from each other; R12 is an alkylene group of 2 to 7 carbon atoms; each of Y and Yxe2x80x2 is hydrogen, a methyl group or a CH2Cl group; Y and Yxe2x80x2 may be the same or different from each other; each of Z and Zxe2x80x2 is oxygen, sulfur or a CH2 group; Z and Zxe2x80x2 may be the same or different from each other; n is an integer of 0 to 15 when Z is oxygen and is 0 when Z is sulfur or a CH2 group; nxe2x80x2 is an integer of 0 to 15 when Zxe2x80x2 is oxygen and is 0 when Zxe2x80x2 is sulfur or a CH2 group; and n and nxe2x80x2 may be the same or different from each other.
The above compound B is preferably hexamethylenediisocyanate, isophoronediisocyanate, hydrogenated tolylenediisocyanate, hydrogenated xylylenediisocyanate, or norbornanediisocyanato methyl.
The extruding auxiliary for a cement material according to the present invention comprises the water-soluble polyurethane.
In the extruding auxiliary for a cement material according to the present invention, the above water-soluble polyurethane is preferably such that its 2.5% aqueous solution has a viscosity at 25xc2x0 C. of 1,000 to 1,000,000 mPaxc2x7s.
The extruding composition of a cement material according to the present invention contains the above extruding auxiliary for a cement material, a hydraulic inorganic powder, a fine aggregate, a fiber and water. The fiber is preferably an asbestos-substitute fiber.
The extruded form of a cement material having improved strength according to the present invention is obtained by extruding the extruding composition of a cement material.
The thickening agent for a mortar (xe2x80x9ca thickening agent for a mortarxe2x80x9d is sometimes referred to as xe2x80x9ca mortar thickening agentxe2x80x9d hereinafter.) according to the present invention comprises the above water-soluble polyurethane.
In the mortar thickening agent according to the present invention the above water-soluble polyurethane is preferably such that the molar ratio of the above repeating unit (U-1), which has the general formula (1), is 0.5 or higher and 0.99 or lower, the molar ratio of the above repeating unit (U-2), which has the general formula (2), is 0.01 or higher and 0.5 or lower, and that its 2% aqueous solution has a viscosity in the range of 10 mPaxc2x7s to 300,000 mPaxc2x7s at 20xc2x0 C.
In the mortar thickening agent according to the present invention, the above water-soluble polyalkylene polyol is preferably polyethylene glycol having a number average molecular weight of 1,000 to 20,000.
In the mortar thickening agent according to the present invention, the above polyisocyanate compound is preferably a chain aliphatic diisocyanate or an alicyclic diisocyanate. And the above polyisocyanate compound is a preferably compound selected from the group consisting of hexamethylenediisocyanate, isophoronediisocyanate, hydrogenated tolylenediisocyanate, hydrogenated xylylenediisocyanate, and norbornanediisocyanato methyl.
In the mortar thickening agent according to the present invention, the above compound D is preferably a comb-shaped hydrophobic diol represented by the following general formula (6): 
wherein R13 is a straight-chain or chain-branched alkyl group having 4 to 18 carbon atoms, each of R14 and R15 is a straight-chain or branched chain alkyl group of 4 to 18 carbon atoms, and the alkyl groups R14 and R15 may be the same or different from each other.
The dry mortar composition according to the present invention comprises the above mortar thickening agent and a hydraulic inorganic powder.
The mortar composition according to the present invention comprises the above mortar thickening agent, a hydraulic inorganic powder and water.
A thickening agent for the underwater concrete (xe2x80x9ca thickening agent for an underwater concretexe2x80x9d is sometimes referred to as xe2x80x9can underwater thickening agentxe2x80x9d hereinafter.) according to the present invention comprises the above water-soluble polyurethane.
In the above underwater concrete thickening agent, the above water-soluble polyurethane is preferably such that the molar ratio of the above repeating unit (U-1), which has the general formula (1), is 0.5 or higher and 0.99 or lower, the molar ratio of the above repeating unit (U-2), which has the general formula (2), is 0.01 or higher and 0.5 or lower, and that its weight average molecular weight measured by GPC is in the range of 100,000 to 1,000,000.
In the above underwater concrete thickening agent, the above compound D is preferably a comb-shaped hydrophobic diol represented by the following formula (4): 
wherein R1xe2x80x2 is a chain alkyl group of 4 to 18 carbon atoms, each of R2xe2x80x2 and R3xe2x80x2 is an alkyl group or aryl group of 4 to 18 carbon atoms, the total number of carbon atoms of R1xe2x80x2, R2xe2x80x2 and R3xe2x80x2 is 12 to 40, and R2xe2x80x2 and R3xe2x80x2 are the same.
In the above underwater concrete thickening agent, the above polyisocyanate compound is preferably a chain aliphatic diisocyanate or an alicyclic diisocyanate. And the above polyisocyanate compound is preferably a compound selected from the group consisting of hexamethylenediisocyanate, isophoronediisocyanate, hydrogenated tolylenediisocyanate, hydrogenated xylylenediisocyanate, and norbornanediisocyanato methyl.
In the above underwater concrete thickening agent, 2% aqueous solution of the above water-soluble polyurethane preferably has a viscosity at 20xc2x0 C. in the range of 1,000 to 500,000 mPaxc2x7s.
The composition for an underwater concrete (xe2x80x9ca composition for an underwater concretexe2x80x9d is sometimes referred to as xe2x80x9can underwater concrete compositionxe2x80x9d hereinafter.) of the present invention is obtained by adding 0.1 to 10% by weight of the above underwater concrete thickening agent based on 100% by weight of cement.
The ceramics forming binder according to the present invention comprises the above water-soluble polyurethane.
In the above ceramics forming binder, the above water-soluble polyurethane is preferably such that the molar ratio of the above repeating unit (U-1), which has the general formula (1), is 0.5 or higher and 0.99 or lower, the molar ratio of the above repeating unit (U-2), which has the general formula (2), is 0.01 or higher and 0.5 or lower, and that its weight average molecular weight measured by GPC is in the range of 10,000 to 1,000,000.
In the above ceramics forming binder, the above water-soluble polyalkylene polyol is preferably polyethylene glycol having a number average molecular weight of 1,000 to 20,000 and the above polyisocyanate compound is chain aliphatic diisocyanate or an alicyclic diisocyanate.
For the above ceramics forming binder, preferably the above polyisocyanate compound is a compound selected from the group consisting of hexamethylenediisocyanate, isophoronediisocyanate, hydrogenated tolylenediisocyanate, hydrogenated xylylenediisocyanate, and norbornanediisocyanato methyl.
The above ceramics forming binder can be used as a binder for a ceramics extrusion.
The moisturizer for hair cosmetics according to the present invention comprises the above water-soluble polyurethane.
In the above moisturizer for hair cosmetics, the above water-soluble polyurethane is preferably such that the molar ratio of the above repeating unit (U-1), which has the general formula (1), is 0.5 or higher and 0.99 or lower, the molar ratio of the above repeating unit (U-2), which has the general formula (2), is 0.01 or higher and 0.5 or lower, and that its weight average molecular weight measured by the GPC is in the range of 10,000 to 1,000,000.
In the above moisturizer for hair cosmetics, the above water-soluble polyalkylene polyol is preferably polyethylene glycol having a number average molecular weight of 400 to 20,000 and the above polyisocyanate compound is a chain aliphatic diisocyanate or an alicyclic diisocyanate.
In the above moisturizer for hair cosmetics, the above polyisocyanate compound is preferably a compound selected from the group consisting of hexamethylenediisocyanate, isophoronediisocyanate, hydrogenated tolylenediisocyanate, hydrogenated xylylenediisocyanate and norbornanediisocyanato methyl.